Resist composition and patterning process

ABSTRACT

A resist composition comprising a base polymer and a phosphazene salt compound offers a high dissolution contrast, minimal LWR, and dimensional stability on PPD.

CROSS-REFERENCE TO RELATED APPLICATION

This non-provisional application claims priority under 35 U.S.C. §119(a) on Patent Application Nos. 2015-256346 and 2016-135025 filed inJapan on Dec. 28, 2015 and Jul. 7, 2016, respectively, the entirecontents of which are hereby incorporated by reference.

TECHNICAL FIELD

This invention relates to a resist composition comprising a phosphazenesalt compound and a pattern forming process.

BACKGROUND ART

To meet the demand for higher integration density and operating speed ofLSIs, the effort to reduce the pattern rule is in rapid progress. Thewide-spreading flash memory market and the demand for increased storagecapacities drive forward the miniaturization technology. As the advancedminiaturization technology, manufacturing of microelectronic devices atthe 65-nm node by the ArF lithography has been implemented in a massscale. Manufacturing of 45-nm node devices by the next generation ArFimmersion lithography is approaching to the verge of high-volumeapplication. The candidates for the next generation 32-nm node includeultra-high NA lens immersion lithography using a liquid having a higherrefractive index than water in combination with a high refractive indexlens and a high refractive index resist film, EUV lithography ofwavelength 13.5 nm, and double patterning version of the ArFlithography, on which active research efforts have been made.

Chemically amplified resist compositions comprising an acid generatorcapable of generating an acid upon exposure to light or EB includechemically amplified positive resist compositions wherein deprotectionreaction takes place under the action of acid and chemically amplifiednegative resist compositions wherein crosslinking reaction takes placeunder the action of acid. Quenchers are often added to these resistcompositions for the purpose of suppressing the diffusion of the acid tounexposed areas to improve the contrast. The addition of quenchers isfully effective to this purpose. A number of amine quenchers wereproposed as disclosed in Patent Documents 1 to 3.

As the pattern feature size is reduced, approaching to the diffractionlimit of light, light contrast lowers. In the case of positive resistfilm, a lowering of light contrast leads to reductions of resolution andfocus margin of hole and trench patterns.

For mitigating the influence of reduced resolution of resist pattern dueto a lowering of light contrast, an attempt is made to enhance thedissolution contrast of resist film. Another attempt is also made tocontrol acid diffusion which causes image blurs to resist patterns.

There is known a chemically amplified resist material utilizing an acidamplifying mechanism that a compound is decomposed with an acid togenerate another acid. In general, the concentration of acid creeps uplinearly with an increase of exposure dose. In the case of the acidamplifying mechanism, the concentration of acid jumps up non-linearly asthe exposure dose increases. The acid amplifying system is beneficialfor further enhancing the advantages of chemically amplified resist filmincluding high contrast and high sensitivity, but worsens the drawbacksof chemically amplified resist film that environmental resistance isdegraded by amine contamination and maximum resolution is reduced by anincrease of acid diffusion distance. The acid amplifying system is verydifficult to control when implemented in practice.

Another approach for enhanced contrast is by reducing the concentrationof amine with an increasing exposure dose. This may be achieved byapplying a compound which loses the quencher function upon lightexposure.

With respect to the acid labile group used in (meth)acrylate polymersfor the ArF lithography, deprotection reaction takes place when aphotoacid generator capable of generating a sulfonic acid havingfluorine substituted at α-position (referred to “α-fluorinated sulfonicacid”) is used, but not when an acid generator capable of generating asulfonic acid not having fluorine substituted at α-position (referred to“α-non-fluorinated sulfonic acid”) or carboxylic acid is used. If asulfonium or iodonium salt capable of generating an α-fluorinatedsulfonic acid is combined with a sulfonium or iodonium salt capable ofgenerating an α-non-fluorinated sulfonic acid, the sulfonium or iodoniumsalt capable of generating an α-non-fluorinated sulfonic acid undergoesion exchange with the α-fluorinated sulfonic acid. Through the ionexchange, the α-fluorinated sulfonic acid thus generated by lightexposure is converted back to the sulfonium or iodonium salt while thesulfonium or iodonium salt of an α-non-fluorinated sulfonic acid orcarboxylic acid functions as a quencher.

Further, the sulfonium or iodonium salt capable of generating anα-non-fluorinated sulfonic acid also functions as a photodegradablequencher since it loses the quencher function by photodegradation.Non-Patent Document 3 points out that the addition of a photodegradablequencher expands the margin of a trench pattern although the structuralformula is not illustrated. However, it has only a little influence onperformance improvement. There is a desire to have a quencher forfurther improving contrast.

Patent Document 4 discloses a quencher of onium salt type which reducesits basicity through a mechanism that it generates an amino-containingcarboxylic acid upon light exposure, which in turn forms a lactam in thepresence of acid. Due to the mechanism that basicity is reduced underthe action of acid, acid diffusion is controlled by high basicity in theunexposed region where the amount of acid generated is minimal, whereasacid diffusion is promoted due to reduced basicity of the quencher inthe overexposed region where the amount of acid generated is large. Thisexpands the difference in acid amount between the exposed and unexposedregions, from which an improvement in contrast is expected. However,this method has the drawback of increased acid diffusion.

Biguanide and phosphazene compounds are known as superstrong basecompounds. Since they have a higher basicity than diazabicycloundecene(DBU), their use as a catalyst for curing reaction of epoxy compounds isunder study. For example, Patent Documents 5 and 6 disclose basegenerators capable of generating guanidine, biguanide, phosphazene, and2,5,8,9-tetraaza-1-phosphabicyclo[3.3.3]undecane compounds upon lightexposure. In general, the amount of acid generated by a photoacidgenerator increases as the exposure dose is increased. In a system wherea photoacid generator and a photobase generator coexist with the amountsand generation efficiencies of PAG and PBG being equal, the amount ofgenerated acid does not increase even when the exposure dose isincreased. If the amount and generation efficiency of PAG are great, theamount of acid increases as the exposure dose is increased, but thatincrease is yet insufficient and so the contrast of resist is low.

Attention is now paid to the negative tone pattern forming process viaorganic solvent development. In an attempt to form a hole pattern bylight exposure, a hole pattern having the minimum pitch can be formed bya combination of a bright-pattern mask with a negative tone resist.There is the problem that the pattern as developed varies in size due toa lapse of time, known as post exposure bake to development delay(PEBDD) or post PEB delay (PPD). The reason is that during storage ofthe resist film at room temperature after PEB, the acid graduallydiffuses into the unexposed region where deprotection reaction takesplace. One solution to the PPD problem is to use a protective grouphaving a high level of activation energy and to effect PEB at hightemperature. Since PPD is a reaction at room temperature, the influenceof PPD is mitigated as the temperature gap between PEB and PPD isgreater. Use of an acid generator capable of generating an acid having abulky anion is also effective for mitigating the influence of PPD. Whilea proton serving as acid pairs with an anion, the hopping of proton isreduced as the size of anion becomes larger.

Another component that is expected effective for mitigating theinfluence of PPD is a quencher. Conventional quenchers were developedfor the purpose of suppressing acid diffusion during PEB at hightemperature for thereby enhancing the contrast of deprotection reaction.For mitigating the influence of PPD, it is desired from a differentviewpoint to develop a quencher capable of suppressing acid diffusion atroom temperature.

CITATION LIST

-   Patent Document 1: JP-A 2001-194776-   Patent Document 2: JP-A 2002-226470-   Patent Document 3: JP-A 2002-363148-   Patent Document 4: JP-A 2015-090382-   Patent Document 5: JP-A 2010-084144-   Patent Document 6: WO 2015/111640-   Non-Patent Document 1: SPIE Vol. 5039 p 1 (2003)-   Non-Patent Document 2: SPIE Vol. 6520 p 65203L-1 (2007)-   Non-Patent Document 3: SPIE Vol. 7639 p 76390W (2010)

DISCLOSURE OF INVENTION

As alluded to above, the addition of quenchers is effective formitigating the influence of PPD. In the case of base generators capableof generating superstrong bases as disclosed in Patent Documents 5 and6, the site where a base is generated is in the exposed region. When aresist film is allowed to stand at room temperature after PEB, aciddiffusion takes place within the resist film from the exposed region tothe unexposed region. In this situation, the quencher based on themechanism that a base is generated only in the exposed region fails toprevent acid diffusion from the exposed region to the unexposed region.

Such quenchers as amine quenchers and sulfonium and iodonium salts ofsulfonic acid and carboxylic acid have a high basicity and are fullyeffective for suppressing acid diffusion in the unexposed region, buttheir performance is still unsatisfactory. Desired are quenchers capableof suppressing acid diffusion at room temperature, providing a highdissolution contrast, and reducing edge roughness (LWR) rather thanthese quenchers.

An object of the invention is to provide a resist composition whichexhibits a high dissolution contrast, a reduced LWR, and no dimensionalchanges on PPD, independent of whether it is of positive tone ornegative tone; and a pattern forming process using the same.

The inventors have found that using a specific phosphazene salt compoundas the quencher, a resist film having a reduced LWR, a high dissolutioncontrast, and no dimensional changes on PPD is obtainable.

In one aspect, the invention provides a resist composition comprising abase polymer and a phosphazene salt compound having the formula (A).

Herein R¹ to R⁷ are each independently hydrogen, or a C₁-C₂₄ straight,branched or cyclic alkyl group, C₂-C₂₄ straight, branched or cyclicalkenyl group, C₂-C₂₄ straight, branched or cyclic alkynyl group, orC₆-C₂₀ aryl group, which may contain an ester, ether, sulfide,sulfoxide, carbonate, carbamate, sulfone, halogen, amino, amide,hydroxy, thiol or nitro moiety, a pair of R¹ and R², R² and R³, R³ andR⁴, R⁴ and R⁵, R⁵ and R⁶, or R⁶ and R⁷ may bond together to form a ring,or a pair of R² and R³, R⁴ and R⁵, or R⁶ and taken together, may form adouble bond or a group having the formula (A)-1, R¹ may be a grouphaving the formula (A)-2,

wherein R⁸ to R¹⁷ are each independently hydrogen, or a C₁-C₂₄ straight,branched or cyclic alkyl group, C₂-C₂₄ straight, branched or cyclicalkenyl group, C₂-C₂₄ straight, branched or cyclic alkynyl group, orC₆-C₂₉ aryl group, a pair of R⁸ and R⁹, R⁹ and R¹⁰, R¹⁰ and R¹¹, R¹¹ andR¹², R¹² and R¹³, R¹⁴ and R¹⁵, or R¹⁶ and R¹⁷ may bond together to forma ring, or a pair of R⁸ and R⁹, R¹⁰ and R¹¹, or R¹² and R¹³, takentogether, may form a double bond or a group having the formula (A)-1. A⁻is an anion selected from the group consisting of hydroxide, chloride,bromide, iodide, nitrate, nitrite, chlorate, chlorite, perchlorate,hydrogencarbonate, dihydrogenphosphate, hydrogensulfate, thiocyanate,hydrogenoxalate, cyanide, iodate ions, and anions of the formulae (M-1)and (M-2):

wherein R¹⁸ is hydrogen, or a C₁-C₃₀ straight, branched or cyclic alkylgroup, C₂-C₃₀ straight, branched or cyclic alkenyl group, C₂-C₃₀straight, branched or cyclic alkynyl group, C₆-C₂₀ aryl group, C₇-C₂₀aralkyl group, or C₃-C₂₀ aromatic or aliphatic heterocycle-containinggroup, which may contain an ester, ether, sulfide, sulfoxide, carbonate,carbamate, sulfone, halogen, amino, amide, hydroxy, thiol or nitromoiety, with the proviso that R¹⁸ does not contain a group of theformula (A)-3:

wherein Ar is a C₆-C₁₆ aromatic group, R²¹ and R²² are eachindependently hydrogen, hydroxy, alkoxy, C₁-C₆ straight, branched orcyclic alkyl group, or C₆-C₁₀ aryl group, R¹⁹ is fluorine, or a C₁-C₁₀straight, branched or cyclic fluoroalkyl group or fluorophenyl group,which may contain a hydroxy, ether, ester or alkoxy moiety, R²⁰ ishydrogen, or a C₁-C₁₀ straight, branched or cyclic alkyl group, C₂-C₁₀straight, branched or cyclic alkenyl group, C₂-C₁₀ straight or branchedalkynyl group, or C₆-C₁₀ aryl group, which may contain a hydroxy, ether,ester or alkoxy moiety.

In a preferred embodiment, the resist composition may further comprisean acid generator capable of generating sulfonic acid, sulfonimide orsulfonmethide, and/or an organic solvent.

In a preferred embodiment, the base polymer comprises recurring unitshaving the formula (a1) or recurring units having the formula (a2).

Herein R³¹ and R³³ are each independently hydrogen or methyl, R³² andR³⁴ are each independently an acid labile group, X is a single bond,ester group, phenylene group, naphthylene group or a C₁-C₁₂ linkinggroup containing lactone ring, and Y is a single bond or ester group.

In a preferred embodiment, the resist composition may further comprise adissolution inhibitor. Typically the resist composition is a chemicallyamplified positive resist composition.

In another preferred embodiment, the base polymer is free of an acidlabile group; the resist composition may further comprise a crosslinker.Typically the resist composition is a chemically amplified negativeresist composition.

In a preferred embodiment, the base polymer further comprises recurringunits of at least one type selected from the formulae (f1) to (f3).

Herein R⁵¹, R⁵⁵ and R⁵⁹ each are hydrogen or methyl; R⁵² is a singlebond, phenylene, —O—R⁶³—, or —C(═O)—Y¹—R⁶³—, Y¹ is —O— or —NH—, R⁶³ is aC₁-C₆ straight, branched or cyclic alkylene or alkenylene group whichmay contain a carbonyl, ester, ether or hydroxyl moiety, or phenylenegroup; R⁵³, R⁵⁴, R⁵⁶, R⁵⁷, R⁵⁸, R⁶⁰, R⁶¹, and R⁶² are each independentlya C₁-C₁₂ straight, branched or cyclic alkyl group which may contain acarbonyl, ester or ether moiety, or a C₆-C₁₂ aryl group, C₇-C₂₀ aralkylgroup or mercaptophenyl group; A¹ is a single bond, -A⁰-C(═O)—O—, -A⁰-O—or -A⁰-O—C(═O)—, A⁰ is a C₁-C₁₂ straight, branched or cyclic alkylenegroup which may contain a carbonyl, ester or ether moiety; A² ishydrogen or trifluoromethyl; Z¹ is a single bond, methylene, ethylene,phenylene, fluorinated phenylene, —O—R⁶⁴—, or —C(═O)—Z²—R⁶⁴—, Z² is —O—or —NH—, R⁶⁴ is a C₁-C₆ straight, branched or cyclic alkylene oralkenylene group which may contain a carbonyl, ester, ether or hydroxylmoiety, or phenylene, fluorinated phenylene ortrifluoromethyl-substituted phenylene group; M⁻ is a non-nucleophiliccounter ion, and f1, f2 and f3 are numbers in the range: 0≤f1≤0.5,0≤f2≤0.5, 0≤f3≤0.5, and 0<f1+f2+f3≤0.5.

The resist composition may further comprise a surfactant.

In another aspect, the invention provides a process for forming apattern comprising the steps of applying the resist composition definedabove onto a substrate, baking to form a resist film, exposing theresist film to high-energy radiation, and developing the exposed film ina developer.

In a preferred embodiment, the high-energy radiation is ArF excimerlaser radiation of wavelength 193 nm, KrF excimer laser radiation ofwavelength 248 nm, EB, or EUV of wavelength 3 to 15 nm.

Advantageous Effects of Invention

Since a resist film containing a specific phosphazene salt compoundexhibits an acid diffusion suppressing effect and a high dissolutioncontrast, it offers improved resolution, a wide focus margin, a reducedLWR, and no dimensional changes on PPD as a positive or negative toneresist film subject to alkaline development and as a negative toneresist film subject to organic solvent development.

DESCRIPTION OF EMBODIMENTS

As used herein, the singular forms “a,” “an” and “the” include pluralreferents unless the context clearly dictates otherwise. The notation(C_(n)-C_(m)) means a group containing from n to m carbon atoms pergroup. Me stands for methyl, Ac for acetyl, and Ph for phenyl.

The abbreviations and acronyms have the following meaning.

EB: electron beam

EUV: extreme ultraviolet

Mw: weight average molecular weight

Mn: number average molecular weight

Mw/Mn: molecular weight distribution or dispersity

GPC: gel permeation chromatography

PEB: post-exposure bake

PPD: post PEB delay

PAG: photoacid generator

LWR: line width roughness

Resist Composition

The resist composition of the invention is defined as comprising a basepolymer and a specific phosphazene salt compound. The phosphazene saltcompound undergoes ion exchange with sulfonic acid, sulfonimide orsulfonmethide generated by an acid generator, especially sulfonic acidhaving a fluorinated alkyl group, bissulfonimide or trissulfonmethide,to form a salt and release carboxylic acid or sulfonamide. Because ofits very high basicity, the phosphazene compound has a high acidtrapping ability and acid diffusion suppressing effect. Since thephosphazene salt compound is not photosensitive, it does not convert toa phosphazene compound upon receipt of light and maintains a sufficientacid trapping ability even in the unexposed region. Thus it helpssuppress acid diffusion from the exposed region to the unexposed region.

While the resist composition of the invention should essentially containthe phosphazene salt compound, another amine compound, ammonium salt,sulfonium salt or iodonium salt may be separately added as the quencher.Examples of the ammonium, sulfonium or iodonium salt to be added as thequencher include sulfonium or iodonium salts of carboxylic acid,sulfonic acid, sulfonamide and saccharin. The carboxylic acid usedherein may or may not be fluorinated at α-position.

The phosphazene salt compound exerts an acid diffusion suppressingeffect and contrast enhancing effect, which may stand good either inpositive and negative tone pattern formation by alkaline development orin negative tone pattern formation by organic solvent development.

Phosphazene Salt Compound

The phosphazene salt compound to be included in the inventive resistcomposition has the following formula (A).

In formula (A), R¹ to R⁷ are each independently hydrogen, or a C₁-C₂₄straight, branched or cyclic alkyl group, C₂-C₂₄ straight, branched orcyclic alkenyl group, C₂-C₂₄ straight, branched or cyclic alkynyl group,or C₆-C₂₀ aryl group, which may contain an ester, ether, sulfide,sulfoxide, carbonate, carbamate, sulfone, halogen, amino, amide,hydroxy, thiol or nitro moiety, a pair of R¹ and R², R² and R³, R³ andR⁴, R⁴ and R⁵, R⁵ and R⁶, or R⁶ and R⁷ may bond together to form a ring,or a pair of R² and R³, R⁴ and R⁵, or R⁶ and R⁷, taken together, mayform a double bond or a group having the formula (A)-1, R¹ may be agroup having the formula (A)-2.

Herein R⁸ to R¹⁷ are each independently hydrogen, or a C₁-C₂₄ straight,branched or cyclic alkyl group, C₂-C₂₄ straight, branched or cyclicalkenyl group, C₂-C₂₄ straight, branched or cyclic alkynyl group, orC₆-C₂₀ aryl group, a pair of R⁸ and R⁹, R⁹ and R¹⁰, R¹⁰ and R¹¹, R¹¹ andR¹², R¹² and R¹³, R¹⁴ and R¹⁵, or R¹⁶ and R¹⁷ may bond together to forma ring, or a pair of R⁸ and R⁹, R¹⁰ and R¹¹, or R¹² and R¹³, takentogether, may form a double bond or a group having the formula (A)-1.

In formula (A), A⁻ is an anion selected from among hydroxide, chloride,bromide, iodide, nitrate, nitrite, chlorate, chlorite, perchlorate,hydrogencarbonate, dihydrogenphosphate, hydrogensulfate, thiocyanate,hydrogenoxalate, cyanide, iodate ions, and anions of the formulae (M-1)and (M-2).

In formula (M-1), R¹⁸ is hydrogen, or a C₁-C₃₀ straight, branched orcyclic alkyl group, C₂-C₃₀ straight, branched or cyclic alkenyl group,C₂-C₃₀ straight, branched or cyclic alkynyl group, C₅-C₂₀ aryl group,C₇-C₂₀ aralkyl group, or C₃-C₂₀ aromatic or aliphaticheterocycle-containing group, which may contain an ester, ether,sulfide, sulfoxide, carbonate, carbamate, sulfone, halogen, amino,amide, hydroxy, thiol or nitro moiety, with the proviso that R¹⁸ doesnot contain a group of the formula (A)-3:

wherein Ar is a C₆-C₁₆ aromatic group, R²¹ and R²² are eachindependently hydrogen, hydroxy, alkoxy, C₁-C₆ straight, branched orcyclic alkyl group, or C₆-C₁₀ aryl group. In formula (M-2), R¹⁹ isfluorine, or a C₁-C₁₃ straight, branched or cyclic fluoroalkyl group orfluorophenyl group, which may contain a hydroxy, ether, ester or alkoxymoiety. R²⁰ is hydrogen, or a C₁-C₁₀ straight, branched or cyclic alkylgroup, C₂-C₁₀ straight, branched or cyclic alkenyl group, C₂-C₁₀straight or branched alkynyl group, or C₅-C₁₃ aryl group, which maycontain a hydroxy, ether, ester or alkoxy moiety.

Examples of the carboxylate anion having formula (M-1) are given below,but not limited thereto.

Examples of the sulfonamide anion having formula (M-2) are given below,but not limited thereto.

Examples of the cation in the phosphazene salt compound having formula(A) are given below, but not limited thereto.

The phosphazene cation has a positive charge which is delocalized on thephosphorus atom and surrounding nitrogen atoms. This means that the siteof trapping an anion of sulfonic acid, sulfonimide or sulfonmethide forneutralization is present everywhere so that the anion may be quicklytrapped. Therefore, the phosphazene salt compound is a superior quencherhaving a high trapping ability as well as a high basicity.

The phosphazene salt compound having formula (A) may be synthesized, forexample, by mixing a phosphazene compound with a carboxylic acid orsulfonamide.

In the resist composition, the phosphazene salt compound having formula(A) is preferably used in an amount of 0.001 to 50 parts, morepreferably 0.01 to 20 parts by weight per 100 parts by weight of thebase polymer, as viewed from sensitivity and acid diffusion suppressingeffect.

Base Polymer

Where the resist composition is of positive tone, the base polymercomprises recurring units containing an acid labile group, preferablyrecurring units having the formula (a1) or recurring units having theformula (a2). These units are simply referred to as recurring units (a1)and (a2).

Herein R³¹ and R³³ are each independently hydrogen or methyl. R³² andR³⁴ are each independently an acid labile group. X is a single bond,ester group, phenylene group, naphthylene group or a C₁-C₁₂ linkinggroup containing lactone ring, with a single bond, phenylene ornaphthylene being preferred. Y is a single bond or ester group, with asingle bond being preferred.

Examples of the recurring units (a1) are shown below, but not limitedthereto. R³¹ and R³² are as defined above.

The acid labile groups represented by R³² and R³⁴ in the recurring units(a1) and (a2) may be selected from a variety of such groups. The acidlabile groups may be the same or different and include those groupsdescribed in JP-A 2013-080033 (U.S. Pat. No. 8,574,817) and JP-A2013-083821 (U.S. Pat. No. 8,846,303), for example. The preferred acidlabile groups include groups of the following formulae (AL-1) to (AL-3).

In formulae (AL-1) and (AL-2), R³⁵ and R³⁸ are each independently aC₁-C₄₀, preferably C₁-C₂₀ monovalent hydrocarbon group, typicallystraight, branched or cyclic alkyl, which may contain a heteroatom suchas oxygen, sulfur, nitrogen or fluorine. R³⁶ and R³⁷ are eachindependently hydrogen or a C₁-C₂₀ monovalent hydrocarbon group,typically straight, branched or cyclic alkyl, which may contain aheteroatom such as oxygen, sulfur, nitrogen or fluorine. A1 is aninteger of 0 to 10, especially 1 to 5. A pair of and R³⁷, R³⁶ and R⁹⁸,or R³⁷ and R³⁸ may bond together to form a ring, typically alicyclic,with the carbon atom or carbon and oxygen atoms to which they areattached, the ring containing 3 to 20 carbon atoms, preferably 4 to 16carbon atoms.

In formula (AL-3), R³⁹, R⁴⁰ and R⁴¹ are each independently a C₁-C₂₀monovalent hydrocarbon group, typically straight, branched or cyclicalkyl, which may contain a heteroatom such as oxygen, sulfur, nitrogenor fluorine. A pair of R³⁹ and R⁴⁰, R³⁹ and R⁴¹, or R⁴⁰ and R⁴¹ may bondtogether to form a ring, typically alicyclic, with the carbon atom towhich they are attached, the ring containing 3 to 20 carbon atoms,preferably 4 to 16 carbon atoms.

The base polymer may further comprise recurring units (b) having aphenolic hydroxyl group as an adhesive group. Examples of suitablemonomers from which recurring units (b) are derived are given below, butnot limited thereto.

Further, recurring units (c) having another adhesive group selected fromhydroxyl (other than phenolic hydroxyl), lactone ring, ether, ester,carbonyl and cyano groups may also be incorporated in the base polymer.Examples of suitable monomers from which recurring units (c) are derivedare given below, but not limited thereto.

In the case of a monomer having a hydroxyl group, the hydroxyl group maybe replaced by an acetal group susceptible to deprotection with acid,typically ethoxyethoxy, prior to polymerization, and the polymerizationbe followed by deprotection with weak acid and water. Alternatively, thehydroxyl group may be replaced by an acetyl, formyl, pivaloyl or similargroup prior to polymerization, and the polymerization be followed byalkaline hydrolysis.

In another preferred embodiment, the base polymer may further compriserecurring units (d) selected from units of indene, benzofuran,benzothiophene, acenaphthylene, chromone, coumarin, and norbornadiene,or derivatives thereof. Suitable monomers are exemplified below.

Besides the recurring units described above, further recurring units (e)may be incorporated in the base polymer, examples of which includestyrene, vinylnaphthalene, vinylanthracene, vinylpyrene,methyleneindene, vinylpyridine, and vinylcarbazole.

In a further embodiment, recurring units (f) derived from an onium salthaving a polymerizable carbon-carbon double bond may be incorporated inthe base polymer. JP-A 2005-084365 discloses sulfonium and iodoniumsalts having a polymerizable carbon-carbon double bond capable ofgenerating a sulfonic acid. JP-A 2006-178317 discloses a sulfonium salthaving sulfonic acid directly attached to the main chain.

In a preferred embodiment, the base polymer may further compriserecurring units of at least one type selected from formulae (f1), (f2)and (f3). These units are simply referred to as recurring units (f1),(f2) and (f3), which may be used alone or in combination of two or moretypes.

Herein R⁵¹, R⁵⁵ and R⁵⁹ each are hydrogen or methyl. R⁵² is a singlebond, phenylene, —O—R⁶³—, or —C(═O)—Y¹—R⁶³—, wherein Y¹ is —O— or —NH—,and R⁶³ is a C₁-C₆ straight, branched or cyclic alkylene or alkenylenegroup which may contain a carbonyl, ester, ether or hydroxyl moiety, orphenylene group. R⁵³, R⁵⁴, R⁵⁶, R⁵⁷, R⁵⁸, R⁶⁰, R⁶¹, and R⁶² are eachindependently a C₁-C₁₂ straight, branched or cyclic alkyl group whichmay contain a carbonyl, ester or ether moiety, or a C₆-C₁₂ aryl group,C₇-C₂₀ aralkyl group or mercaptophenyl group. A¹ is a single bond,-A⁰-C(═O)—O—, -A⁰-O— or -A⁰-O—C(═O)—, wherein A⁰ is a C₁-C₁₂ straight,branched or cyclic alkylene group which may contain a carbonyl, ester orether moiety. A² is hydrogen or trifluoromethyl. Z¹ is a single bond,methylene, ethylene, phenylene, fluorinated phenylene, —O—R⁶⁴—, or—C(═O)—Z²—R⁶⁴—, wherein Z² is —O— or —NH—, and R⁶⁴ is a C₁-C₆ straight,branched or cyclic alkylene or alkenylene group which may contain acarbonyl, ester, ether or hydroxyl moiety, or phenylene, fluorinatedphenylene or trifluoromethyl-substituted phenylene group. M⁻ is anon-nucleophilic counter ion, and f1, f2 and f3 are numbers in therange: 0≤f1≤0.5, 0≤f2≤0.5, 0≤f3≤0.5, and 0<f1+f2+f3≤0.5.

Examples of the monomer from which recurring unit (f1) is derived areshown below, but not limited thereto. M⁻ is as defined above.

Examples of the non-nucleophilic counter ion M⁻ include halide ions suchas chloride and bromide ions; fluoroalkylsulfonate ions such astriflate, 1,1,1-trifluoroethanesulfonate, and nonafluorobutanesulfonate;arylsulfonate ions such as tosylate, benzenesulfonate,4-fluorobenzenesulfonate, and 1,2,3,4,5-pentafluorobenzenesulfonate;alkylsulfonate ions such as mesylate and butanesulfonate; sulfonimidessuch as bis(trifluoromethylsulfonyl)imide,bis(perfluoroethylsulfonyl)imide and bis(perfluorobutylsulfonyl)imide;sulfonmethides such as tris(trifluoromethylsulfonyl)methide andtris(perfluoroethylsulfonyl)methide.

Also included are sulfonate ions having fluorine substituted atα-position as represented by the formula (K-1) and sulfonate ions havingfluorine substituted at α- and β-positions as represented by the formula(K-2).

In formula (K-1), R⁶⁵ is hydrogen, or a C₁-C₂₀ straight, branched orcyclic alkyl group, C₂-C₂₀ straight, branched or cyclic alkenyl group,or C₆-C₂₀ aryl group, which may have an ether, ester, carbonyl moiety,lactone ring, or fluorine atom. In formula (K-2), R⁶⁶ is hydrogen, or aC₁-C₃₀ straight, branched or cyclic alkyl or acyl group, C₂-C₂₀straight, branched or cyclic alkenyl group, or C₆-C₂₀ aryl or aryloxygroup, which may have an ether, ester, carbonyl moiety or lactone ring.

Examples of the monomer from which recurring unit (f2) is derived areshown below, but not limited thereto.

Examples of the monomer from which recurring unit (f3) is derived areshown below, but not limited thereto.

The attachment of an acid generator to the polymer main chain iseffective in restraining acid diffusion, thereby preventing a reductionof resolution due to blur by acid diffusion. Also roughness (LWR) isimproved since the acid generator is uniformly distributed. Where a basepolymer containing recurring units of at least one type selected fromrecurring units (f1) to (f3) is used, the addition of a separate PAG maybe omitted.

The base polymer for formulating the positive resist compositioncomprises recurring units (a1) or (a2) having an acid labile group asessential component and additional recurring units (b), (c), (d), (e),(f1), (f2) and (f3) as optional components. A fraction of units (a1),(a2), (b), (c), (d), (e), (f1), (f2) and (f3) is: preferably 0≤a1<1.0,0≤a2<1.0, 0<a1+a2<1.0, 0≤b≤0.9, 0≤c≤0.9, 0≤d≤0.8, 0≤e≤0.8, 0≤f1≤0.5,0≤f2≤0.5, and 0≤f3≤0.5; more preferably 0≤a1≤0.9, 0≤a2≤0.9,0.1≤a1+a2≤0.9, 0≤b≤0.8, 0≤c≤0.8, 0≤d≤0.7, 0≤e≤0.7, 0≤f1≤0.4, 0≤f2≤0.4,and 0≤f3≤0.4; and even more preferably 0≤a1≤0.8, 0≤a2≤0.8,0.1≤a1+a2≤0.8, 0≤b≤0.75, 0≤c≤0.75, 0≤d≤0.6, 0≤e≤0.6, 0≤f1≤0.3, 0≤f2≤0.3,and 0≤f3≤0.3. Note a1+a2+b+c+d+e+f1+f2+f3=1.0.

For the base polymer for formulating the negative resist composition, anacid labile group is not necessarily essential. The base polymercomprises recurring units (b), and optionally recurring units (c), (d),(e), (f1), (f2) and/or (f3). A fraction of these units is: 0<b≤1.0,0≤c≤0.9, 0≤d≤0.8, 0≤e≤0.8, 0≤f1≤0.5, 0≤f2≤0.5, and 0≤f3≤0.5; preferably0.2≤b≤1.0, 0≤c≤0.8, 0≤d≤0.7, 0≤e≤0.7, 0≤f1≤0.4, 0≤f2≤0.4, and 0≤f3≤0.4;and more preferably 0.3≤b≤1.0, 0≤c≤0.75, 0≤d≤0.6, 0≤e≤0.6, 0≤f1≤0.3,0≤f2≤0.3, and 0≤f3≤0.3. Note b+c+d+e+f1+f2+f3=1.0.

The base polymer may be synthesized by any desired methods, for example,by dissolving one or more monomers selected from the monomerscorresponding to the foregoing recurring units in an organic solvent,adding a radical polymerization initiator thereto, and effecting heatpolymerization. Examples of the organic solvent which can be used forpolymerization include toluene, benzene, tetrahydrofuran, diethyl etherand dioxane. Examples of the polymerization initiator used hereininclude 2,2′-azobisisobutyronitrile (AIBN),2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide.Preferably the system is heated at 50 to 80° C. for polymerization totake place. The reaction time is 2 to 100 hours, preferably 5 to 20hours.

When hydroxystyrene or hydroxyvinylnaphthalene is copolymerized, analternative method is possible. Specifically, acetoxystyrene oracetoxyvinylnaphthalene is used instead of hydroxystyrene orhydroxyvinylnaphthalene, and after polymerization, the acetoxy group isdeprotected by alkaline hydrolysis as mentioned above, for therebyconverting the polymer product to hydroxystyrene orhydroxyvinylnaphthalene. For alkaline hydrolysis, a base such as aqueousammonia or triethylamine may be used. The reaction temperature is −20°C. to 100° C., preferably 0° C. to 60° C., and the reaction time is 0.2to 100 hours, preferably 0.5 to 20 hours.

The base polymer should preferably have a weight average molecularweight (Mw) in the range of 1,000 to 500,000, and more preferably 2,000to 30,000, as measured by GPC versus polystyrene standards usingtetrahydrofuran as a solvent. With too low a Mw, the resist compositionmay become less heat resistant. A polymer with too high a Mw may losealkaline solubility and give rise to a footing phenomenon after patternformation.

If a base polymer has a wide molecular weight distribution or dispersity(Mw/Mn), which indicates the presence of lower and higher molecularweight polymer fractions, there is a possibility that foreign matter isleft on the pattern or the pattern profile is degraded. The influencesof Mw and dispersity become stronger as the pattern rule becomes finer.Therefore, the base polymer should preferably have a narrow dispersity(Mw/Mn) of 1.0 to 2.0, especially 1.0 to 1.5, in order to provide aresist composition suitable for micropatterning to a small feature size.

It is understood that a blend of two or more polymers which differ incompositional ratio, Mw or Mw/Mn is acceptable.

Acid Generator

To the resist composition comprising the base polymer and thephosphazene salt compound having formula (A), an acid generator may beadded so that the composition may function as a chemically amplifiedpositive resist composition or chemically amplified negative resistcomposition. The acid generator is typically a compound (PAG) capable ofgenerating an acid upon exposure to actinic ray or radiation. Althoughthe PAG used herein may be any compound capable of generating an acidupon exposure to high-energy radiation, those compounds capable ofgenerating sulfonic acid, sulfonimide or sulfonmethide are preferred.Suitable PAGs include sulfonium salts, iodonium salts,sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate acidgenerators. Exemplary PAGs are described in JP-A 2008-111103, paragraphs[0122]-[0142] (U.S. Pat. No. 7,537,880).

As the PAG used herein, those having the formulae (1) and (2) arepreferred.

In formula (1), R¹⁰¹, R¹⁰² and R¹⁰³ are each independently a C₁-C₂₀straight, branched or cyclic monovalent hydrocarbon group which maycontain a heteroatom. Any two of R¹⁰¹, R¹⁰² and R¹⁰³ may bond togetherto form a ring with the sulfur atom to which they are attached.

In formula (1), X⁻ is an anion of the following formula (1A), (1B), (1C)or (1D).

In formula (1A), R^(fa) is fluorine or a C₁-C₄₀ straight, branched orcyclic monovalent hydrocarbon group which may contain a heteroatom.

Of the anions of formula (1A), an anion having the formula (1A′) ispreferred.

In formula (1A′), R¹⁰⁴ is hydrogen or trifluoromethyl, preferablytrifluoromethyl. R¹⁰⁵ is a C₁-C₃₈ straight, branched or cyclicmonovalent hydrocarbon group which may contain a heteroatom. As theheteroatom, oxygen, nitrogen, sulfur and halogen atoms are preferred,with oxygen being most preferred. Of the monovalent hydrocarbon groupsrepresented by R¹⁰⁵, those groups of 6 to 30 carbon atoms are preferredfrom the aspect of achieving a high resolution in forming patterns offine feature size. Suitable monovalent hydrocarbon groups include, butare not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,s-butyl, t-butyl, pentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl,3-cyclohexenyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl,pentadecyl, heptadecyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl,norbornyl, norbornylmethyl, tricyclodecanyl, tetracyclododecanyl,tetracyclododecanylmethyl, dicyclohexylmethyl, eicosanyl, allyl, benzyl,diphenylmethyl, tetrahydrofuryl, methoxymethyl, ethoxymethyl,methylthiomethyl, acetamidomethyl, trifluoromethyl,(2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl,2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl. In these groups,one or more hydrogen atoms may be substituted by a moiety containing aheteroatom such as oxygen, sulfur, nitrogen or halogen, or a moietycontaining a heteroatom such as oxygen, sulfur or nitrogen may intervenebetween carbon atoms, so that the group may contain a hydroxyl, cyano,carbonyl, ether, ester, sulfonic acid ester, carbonate, lactone ring,sulfone ring, carboxylic anhydride or haloalkyl moiety.

With respect to the synthesis of the sulfonium salt having an anion offormula (1A′), reference may be made to JP-A 2007-145797, JP-A2008-106045, JP-A 2009-007327, and JP-A 2009-258695. Also useful are thesulfonium salts described in JP-A 2010-215608, JP-A 2012-041320, JP-A2012-106986, and JP-A 2012-153644.

Examples of the sulfonium salt having an anion of formula (1A) are shownbelow, but not limited thereto.

In formula (1B), R^(fb1) and R^(fb2) are each independently fluorine ora C₁-C₄₀ straight, branched or cyclic monovalent hydrocarbon group whichmay contain a heteroatom. Illustrative examples of the monovalenthydrocarbon group are as exemplified for R¹⁰⁵. Preferably R^(fb1) andR^(fb2) are fluorine or C₁-C₄ straight fluorinated alkyl groups. Also,R^(fb1) and R^(fb2) may bond together to form a ring with the linkage:—CF₂—SO₂—N⁻—SO₂—CF₂— to which they are attached. It is preferred to forma ring structure via a fluorinated ethylene or fluorinated propylenegroup.

In formula (1C), R^(fc1), R^(fc2) and R^(fc3) are each independentlyfluorine or a C₁-C₄₀ straight, branched or cyclic monovalent hydrocarbongroup which may contain a heteroatom. Illustrative examples of themonovalent hydrocarbon group are as exemplified for R¹⁰⁵. PreferablyR^(fc1), R^(fc2) and R^(fc3) are fluorine or C₁-C₄ straight fluorinatedalkyl groups. Also, R^(fc1) and R^(fc2) may bond together to form a ringwith the linkage: —CF₂—SO₂—C⁻—SO₂—CF₂— to which they are attached. It ispreferred to form a ring structure via a fluorinated ethylene orfluorinated propylene group.

In formula (1D), R^(fd) is a C₁-C₄₀ straight, branched or cyclicmonovalent hydrocarbon group which may contain a heteroatom.Illustrative examples of the monovalent hydrocarbon group are asexemplified for R¹⁰⁵.

With respect to the synthesis of the sulfonium salt having an anion offormula (1D), reference may be made to JP-A 2010-215608 and JP-A2014-133723.

Examples of the sulfonium salt having an anion of formula (1D) are shownbelow, but not limited thereto.

Notably, the compound having the anion of formula (1D) does not havefluorine at the α-position relative to the sulfo group, but twotrifluoromethyl groups at the β-position. For this reason, it has asufficient acidity to sever the acid labile groups in the resistpolymer. Thus the compound is an effective PAG.

In formula (2), R²⁰¹ and R²⁰² are each independently a C₁-C₃₀ straight,branched or cyclic monovalent hydrocarbon group which may contain aheteroatom. R²⁰³ is a C₁-C₃₀ straight, branched or cyclic divalenthydrocarbon group which may contain a heteroatom. Any two of R²⁰¹, R²⁰²and R²⁰³ may bond together to form a ring with the sulfur atom to whichthey are attached. L^(A) is a single bond, ether group or a C₁-C₂₀straight, branched or cyclic divalent hydrocarbon group which maycontain a heteroatom. X^(A), X^(B), X^(C) and X^(D) are eachindependently hydrogen, fluorine or trifluoromethyl, with the provisothat at least one of X^(A), X^(B), X^(C) and X^(D) is fluorine ortrifluoromethyl, and k is an integer of 0 to 3.

Examples of the monovalent hydrocarbon group include methyl, ethyl,propyl, isopropyl, n-butyl, s-butyl, t-butyl, t-pentyl, n-pentyl,n-hexyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl,2-ethylhexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl,cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl,oxanorbornyl, tricyclo[5.2.1.0^(2,6)]decanyl, adamantyl, phenyl,naphthyl and anthracenyl. In these groups, one or more hydrogen atomsmay be substituted by a moiety containing a heteroatom such as oxygen,sulfur, nitrogen or halogen, or one or more carbon atoms may besubstituted by a moiety containing a heteroatom such as oxygen, sulfuror nitrogen, so that the group may contain a hydroxyl, cyano, carbonyl,ether bond, ester bond, sulfonic acid ester bond, carbonate bond,lactone ring, sulfone ring, carboxylic anhydride or haloalkyl moiety.

Suitable divalent hydrocarbon groups include straight alkane-diyl groupssuch as methylene, ethylene, propane-1,3-diyl, butane-1,4-diyl,pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl,nonane-1,9-diyl, decane-1,10-diyl, undecane-1,11-diyl,dodecane-1,12-diyl, tridecane-1,13-diyl, tetradecane-1,14-diyl,pentadecane-1,15-diyl, hexadecane-1,16-diyl, and heptadecane-1,17-diyl;saturated cyclic divalent hydrocarbon groups such as cyclopentanediyl,cyclohexanediyl, norbornanediyl and adamantanediyl; and unsaturatedcyclic divalent hydrocarbon groups such as phenylene and naphthylene. Inthese groups, one or more hydrogen atom may be replaced by an alkylmoiety such as methyl, ethyl, propyl, n-butyl or t-butyl; one or morehydrogen atom may be replaced by a moiety containing a heteroatom suchas oxygen, sulfur, nitrogen or halogen; or a moiety containing aheteroatom such as oxygen, sulfur or nitrogen may intervene betweencarbon atoms, so that the group may contain a hydroxyl, cyano, carbonyl,ether, ester, sulfonic acid ester, carbonate, lactone ring, sulfonering, carboxylic anhydride or haloalkyl moiety. Of the heteroatoms,oxygen is preferred.

Of the PAGs having formula (2), those having formula (2′) are preferred.

In formula (2′), L^(A) is as defined above. R is hydrogen ortrifluoromethyl, preferably trifluoromethyl. R³⁰¹, R³⁰² and R³⁰³ areeach independently hydrogen or a C₁-C₂₀ straight, branched or cyclicmonovalent hydrocarbon group which may contain a heteroatom. Suitablemonovalent, hydrocarbon groups are as described above for R¹⁰⁵. Thesubscripts x and y are each independently an integer of 0 to 5, and z isan integer of 0 to 4.

Examples of the PAG having formula (2) are shown below, but not limitedthereto. Notably, R is as defined above.

Of the foregoing PAGs, those having an anion of formula (1A′) or (1D)are especially preferred because of reduced acid diffusion and highsolubility in the resist solvent. Also those having an anion of formula(2′) are especially preferred because of extremely reduced aciddiffusion.

The PAG is preferably added in an amount of 0.1 to 50 parts, and morepreferably 1 to 40 parts by weight per 100 parts by weight of the basepolymer.

Other Components

With the phosphazene salt compound having formula (A), the base polymer,and the acid generator, all defined above, other components such as anorganic solvent, surfactant, dissolution inhibitor, and crosslinker maybe blended in any desired combination to formulate a chemicallyamplified positive or negative resist composition. This positive ornegative resist composition has a very high sensitivity in that thedissolution rate in developer of the base polymer in exposed areas isaccelerated by catalytic reaction. In addition, the resist film has ahigh dissolution contrast, resolution, exposure latitude, and processadaptability, and provides a good pattern profile after exposure, andminimal proximity bias because of restrained acid diffusion. By virtueof these advantages, the composition is fully useful in commercialapplication and suited as a pattern-forming material for the fabricationof VLSIs. Particularly when an acid generator is incorporated toformulate a chemically amplified positive resist composition capable ofutilizing acid catalyzed reaction, the composition has a highersensitivity and is further improved in the properties described above.

In the case of positive resist compositions, inclusion of a dissolutioninhibitor may lead to an increased difference in dissolution ratebetween exposed and unexposed regions and a further improvement inresolution. In the case of negative resist compositions, a negativepattern may be formed by adding a crosslinker to reduce the dissolutionrate of the exposed region.

Examples of the organic solvent used herein are described in JP-A2008-111103, paragraphs [0144]-[0145] (U.S. Pat. No. 7,537,880).Exemplary solvents include ketones such as cyclohexanone, cyclopentanoneand methyl-2-n-pentyl ketone; alcohols such as 3-methoxybutanol,3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and1-ethoxy-2-propanol; ethers such as propylene glycol monomethyl ether,ethylene glycol monomethyl ether, propylene glycol monoethyl ether,ethylene glycol monoethyl ether, propylene glycol dimethyl ether, anddiethylene glycol dimethyl ether; esters such as propylene glycolmonomethyl ether acetate (PGMEA), propylene glycol monoethyl etheracetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl3-methoxypropionate, ethyl 3-ethoxypropionate, t-butyl acetate, t-butylpropionate, and propylene glycol mono-t-butyl ether acetate; andlactones such as γ-butyrolactone, which may be used alone or inadmixture.

The organic solvent is preferably added in an amount of 100 to 10,000parts, and more preferably 200 to 8,000 parts by weight per 100 parts byweight of the base polymer.

Exemplary surfactants are described in JP-A 2008-111103, paragraphs[0165]-[0166]. Inclusion of a surfactant may improve or control thecoating characteristics of the resist composition. The surfactant ispreferably added in an amount of 0.0001 to 10 parts by weight per 100parts by weight of the base polymer.

The dissolution inhibitor which can be used herein is a compound havingat least two phenolic hydroxyl groups on the molecule, in which anaverage of from 0 to 100 mol % of all the hydrogen atoms on the phenolichydroxyl groups are replaced by acid labile groups or a compound havingat least one carboxyl group on the molecule, in which an average of 50to 100 mol % of all the hydrogen atoms on the carboxyl groups arereplaced by acid labile groups, both the compounds having a molecularweight of 100 to 1,000, and preferably 150 to 800. Typical are bisphenolA, trisphenol, phenolphthalein, cresol novolac, naphthalenecarboxylicacid, adamantanecarboxylic acid, and cholic acid derivatives in whichthe hydrogen atom on the hydroxyl or carboxyl group is replaced by anacid labile group, as described in U.S. Pat. No. 7,771,914 (JP-A2008-122932, paragraphs [0155]-[0178]).

In the positive resist composition, the dissolution inhibitor ispreferably added in an amount of 0 to 50 parts, more preferably 5 to 40parts by weight per 100 parts by weight of the base polymer.

Suitable crosslinkers which can be used herein include epoxy compounds,melamine compounds, guanamine compounds, glycoluril compounds and ureacompounds having substituted thereon at least one group selected fromamong methylol, alkoxymethyl and acyloxymethyl groups, isocyanatecompounds, azide compounds, and compounds having a double bond such asan alkenyl ether group. These compounds may be used as an additive orintroduced into a polymer side chain as a pendant. Hydroxy-containingcompounds may also be used as the crosslinker.

Of the foregoing crosslinkers, examples of suitable epoxy compoundsinclude tris(2,3-epoxypropyl) isocyanurate, trimethylolmethanetriglycidyl ether, trimethylolpropane triglycidyl ether, andtriethylolethane triglycidyl ether. Examples of the melamine compoundinclude hexamethylol melamine, hexamethoxymethyl melamine, hexamethylolmelamine compounds having 1 to 6 methylol groups methoxymethylated andmixtures thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine,hexamethylol melamine compounds having 1 to 6 methylol groupsacyloxymethylated and mixtures thereof. Examples of the guanaminecompound include tetramethylol guanamine, tetramethoxymethyl guanamine,tetramethylol guanamine compounds having 1 to 4 methylol groupsmethoxymethylated and mixtures thereof, tetramethoxyethyl guanamine,tetraacyloxyguanamine, tetramethylol guanamine compounds having 1 to 4methylol groups acyloxymethylated and mixtures thereof. Examples of theglycoluril compound include tetramethylol glycoluril,tetramethoxyglycoluril, tetramethoxymethyl glycoluril, tetramethylolglycoluril compounds having 1 to 4 methylol groups methoxymethylated andmixtures thereof, tetramethylol glycoluril compounds having 1 to 4methylol groups acyloxymethylated and mixtures thereof. Examples of theurea compound include tetramethylol urea, tetramethoxymethyl urea,tetramethylol urea compounds having 1 to 4 methylol groupsmethoxymethylated and mixtures thereof, and tetramethoxyethyl urea.

Suitable isocyanate compounds include tolylene diisocyanate,diphenylmethane diisocyanate, hexamethylene diisocyanate and cyclohexanediisocyanate. Suitable azide compounds include1,1′-biphenyl-4,4′-bisazide, 4,4′-methylidenebisazide, and4,4′-oxybisazide. Examples of the alkenyl ether group-containingcompound include ethylene glycol divinyl ether, triethylene glycoldivinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinylether, tetramethylene glycol divinyl ether, neopentyl glycol divinylether, trimethylol propane trivinyl ether, hexanediol divinyl ether,1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether,pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitolpentavinyl ether, and trimethylol propane trivinyl ether.

In the negative resist composition, the crosslinker is preferably addedin an amount of 0.1 to 50 parts, more preferably 1 to 40 parts by weightper 100 parts by weight of the base polymer.

In the resist composition of the invention, a quencher other than thephosphazene salt compound having formula (A) may be blended. The otherquencher is typically selected from conventional basic compounds.Conventional basic compounds include primary, secondary, and tertiaryaliphatic amines, mixed amines, aromatic amines, heterocyclic amines,nitrogen-containing compounds with carboxyl group, nitrogen-containingcompounds with sulfonyl group, nitrogen-containing compounds withhydroxyl group, nitrogen-containing compounds with hydroxyphenyl group,alcoholic nitrogen-containing compounds, amide derivatives, imidederivatives, and carbamate derivatives. Also included are primary,secondary, and tertiary amine compounds, specifically amine compoundshaving a hydroxyl, ether, ester, lactone ring, cyano, or sulfonic acidester group as described in JP-A 2008-111103, paragraphs [0146]-[0164],and compounds having a carbamate group as described in JP 3790649.Addition of a basic compound may be effective for further suppressingthe diffusion rate of acid in the resist film or correcting the patternprofile.

Onium salts such as sulfonium salts, iodonium salts and ammonium saltsof sulfonic acids which are not fluorinated at α-position as describedin US 2008153030 (JP-A 2008-158339) and similar onium salts ofcarboxylic acid may also be used as the other quencher. While anα-fluorinated sulfonic acid, sulfonimide, and sulfonmethide arenecessary to deprotect the acid labile group of carboxylic acid ester,an α-non-fluorinated sulfonic acid and a carboxylic acid are released bysalt exchange with an α-non-fluorinated onium salt. An α-non-fluorinatedsulfonic acid and a carboxylic acid function as a quencher because theydo not induce deprotection reaction.

Also useful are quenchers of polymer type as described in U.S. Pat. No.7,598,016 (JP-A 2008-239918). The polymeric quencher segregates at theresist surface after coating and thus enhances the rectangularity ofresist pattern. When a protective film is applied as is often the casein the immersion lithography, the polymeric quencher is also effectivefor preventing a film thickness loss of resist pattern or rounding ofpattern top.

The other quencher is preferably added in an amount of 0 to 5 parts,more preferably 0 to 4 parts by weight per 100 parts by weight of thebase polymer.

To the resist composition, a polymeric additive (or water repellencyimprover) may also be added for improving the water repellency onsurface of a resist film as spin coated. The water repellency improvermay be used in the topcoatless immersion lithography. Suitable waterrepellency improvers include polymers having a fluoroalkyl group andpolymers having a specific structure with a1,1,1,3.3.3-hexafluoro-2-propanol residue and are described in JP-A2007-297590 and JP-A 2008-111103, for example. The water repellencyimprover to be added to the resist composition should be soluble in theorganic solvent as the developer. The water repellency improver ofspecific structure with a 1,1,1,3.3.3-hexafluoro-2-propanol residue iswell soluble in the developer. A polymer having an amino group or aminesalt copolymerized as recurring units may serve as the water repellentadditive and is effective for preventing evaporation of acid during PEB,thus preventing any hole pattern opening failure after development. Anappropriate amount of the water repellency improver is 0 to 20 parts,preferably 0.5 to 10 parts by weight per 100 parts by weight of the basepolymer.

Also, an acetylene alcohol may be blended in the resist composition.Suitable acetylene alcohols are described in JP-A 2008-122932,paragraphs [0179]-[0182]. An appropriate amount of the acetylene alcoholblended is 0 to 5 parts by weight per 100 parts by weight of the basepolymer.

Process

The resist composition is used in the fabrication of various integratedcircuits. Pattern formation using the resist composition may beperformed by well-known lithography processes. The process generallyinvolves coating, prebaking, exposure, post-exposure baking (PEB), anddevelopment. If necessary, any additional steps may be added.

For example, the positive resist composition is first applied onto asubstrate on which an integrated circuit is to be formed (e.g., Si,SiO₂, SiN, SiON, TiN, WSi, BPSG, SOG, or organic antireflective coating)or a substrate on which a mask circuit is to be formed (e.g., Cr, CrO,CrON, or MoSi₂) by a suitable coating technique such as spin coating,roll coating, flow coating, dipping, spraying or doctor coating. Thecoating is prebaked on a hot plate at a temperature of 60 to 150° C. for10 seconds to 30 minutes, preferably 80 to 120° C. for 30 seconds to 20minutes. The resulting resist film is generally 0.1 to 2.0 μm thick.

The resist film is then exposed to a desired pattern of high-energyradiation such as UV, deep-UV, EB, EUV, x-ray, soft x-ray, excimer laserlight, γ-ray or synchrotron radiation, directly or through a mask. Theexposure dose is preferably about 1 to 200 mJ/cm², more preferably about10 to 100 mJ/cm², or about 0.1 to 100 μC/cm², more preferably about 0.5to 50 μC/cm². The resist film is further baked (PEB) on a hot plate at60 to 150° C. for 10 seconds to 30 minutes, preferably 80 to 120° C. for30 seconds to 20 minutes.

Thereafter the resist film is developed with a developer in the form ofan aqueous base solution for 3 seconds to 3 minutes, preferably 5seconds to 2 minutes by conventional techniques such as dip, puddle andspray techniques. A typical developer is a 0.1 to 10 wt %, preferably 2to 5 wt % aqueous solution of tetramethylammonium hydroxide (TMAH),tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide(TPAH), or tetrabutylammonium hydroxide (TBAH). The resist film in theexposed region is dissolved in the developer whereas the resist film inthe unexposed region is not dissolved. In this way, the desired positivepattern is formed on the substrate. Inversely in the case of negativeresist, the exposed region of resist film is insolubilized and theunexposed region is dissolved in the developer. It is appreciated thatthe resist composition of the invention is best suited formicro-patterning using such high-energy radiation as KrF and ArF excimerlaser, EB, EUV, x-ray, soft x-ray, γ-ray and synchrotron radiation.

In an alternative embodiment, a negative pattern may be formed viaorganic solvent development using a positive resist compositioncomprising a base polymer having an acid labile group. The developerused herein is preferably selected from among 2-octanone, 2-nonanone,2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone,diisobutyl ketone, methylcyclohexanone, acetophenone,methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate,pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate,butyl formate, isobutyl formate, pentyl formate, isopentyl formate,methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate,methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyllactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate,pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate,benzyl acetate, methyl phenylacetate, benzyl formate, phenylethylformate, methyl 3-phenylpropionate, benzyl propionate, ethylphenylacetate, and 2-phenylethyl acetate, and mixtures thereof.

At the end of development, the resist film is rinsed. As the rinsingliquid, a solvent which is miscible with the developer and does notdissolve the resist film is preferred. Suitable solvents includealcohols of 3 to 10 carbon atoms, ether compounds of 8 to 12 carbonatoms, alkanes, alkenes, and alkynes of 6 to 12 carbon atoms, andaromatic solvents. Specifically, suitable alcohols of 3 to 10 carbonatoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol,2-butyl alcohol, isobutyl alcohol, t-butyl alcohol, 1-pentanol,2-pentanol, 3-pentanol, t-pentyl alcohol, neopentyl alcohol,2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol,cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol,3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol,2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol,3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol,4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol,cyclohexanol, and 1-octanol. Suitable ether compounds of 8 to 12 carbonatoms include di-n-butyl ether, diisobutyl ether, di-s-butyl ether,di-n-pentyl ether, diisopentyl ether, di-s-pentyl ether, di-t-pentylether, and di-n-hexyl ether. Suitable alkanes of 6 to 12 carbon atomsinclude hexane, heptane, octane, nonane, decane, undecane, dodecane,methylcyclopentane, dimethylcyclopentane, cyclohexane,methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, andcyclononane. Suitable alkenes of 6 to 12 carbon atoms include hexene,heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene,cycloheptene, and cyclooctene. Suitable alkynes of 6 to 12 carbon atomsinclude hexyne, heptyne, and octyne. The solvents may be used alone orin admixture. Besides the foregoing solvents, aromatic solvents may beused, for example, toluene, xylene, ethylbenzene, isopropylbenzene,t-butylbenzene and mesitylene.

Rinsing is effective for minimizing the risks of resist pattern collapseand defect formation. However, rinsing is not essential. If rinsing isomitted, the amount of solvent used may be reduced.

A hole or trench pattern after development may be shrunk by the thermalflow, RELACS® or DSA process. A hole pattern is shrunk by coating ashrink agent thereto, and baking such that the shrink agent may undergocrosslinking at the resist surface as a result of the acid catalystdiffusing from the resist layer during bake, and the shrink agent mayattach to the sidewall of the hole pattern. The bake is preferably at atemperature of 70 to 180° C., more preferably 80 to 170° C., for a timeof 10 to 300 seconds. The extra shrink agent is stripped and the holepattern is shrunk.

EXAMPLE

Examples of the invention are given below by way of illustration and notby way of limitation. The abbreviation “pbw” is parts by weight. For allpolymers, Mw and Mn are determined by GPC versus polystyrene standardsusing tetrahydrofuran solvent, and dispersity Mw/Mn is computedtherefrom.

Quenchers 1 to 13 in the form of phosphazene salt compounds used hereinhave the following structure. Quenchers 1 to 13 were synthesized bymixing a phosphazene compound to provide the illustrated cation with acarboxylic acid, sulfonimide, nitric acid, hydrochloric acid orhydroiodic acid to provide the illustrated anion.

Synthesis Example

Synthesis of Polymers 1 to 6

Base, polymers were prepared by combining suitable monomers, effectingcopolymerization reaction, thereof in tetrahydrofuran solvent, pouringthe reaction solution into methanol for crystallization, repeatedlywashing with hexane, isolation, and drying. The resulting polymers,designated Polymers 1 to 6, were analyzed for composition by ¹H-NMR, andfor Mw and Mw/Mn by GPC.

Examples and Comparative Examples

Positive or negative resist compositions were prepared by dissolvingeach of the polymers synthesized above and selected components in asolvent in accordance with the recipe shown in Tables 1 and 2, andfiltering through a filter having a pore size of 0.2 μm. The solventcontained 100 ppm of a surfactant FC-4430 (3M-Sumitomo Co., Ltd.). Thecomponents in Tables 1 and 2 are as identified below.

Polymers: Polymers 1 to 6 as Identified Above

Organic Solvents:

propylene glycol monomethyl ether acetate (PGMEA)

propylene glycol monomethyl ether (PGME)

γ-butyrolactone (GBL)

cyclohexanone (CyH)

cyclopentanone (CyP)

Acid Generators: PAG1 to PAG3

Quenchers: Quenchers 1 to 13 as Identified Above,

Comparative Quenchers 1 to 5

Water-Repellent Polymer:

ArF Immersion Lithography Patterning Test

Examples 1-1 to 1-14 and Comparative Examples 1-1 to 1-5

On a substrate (silicon wafer), a spin-on carbon film ODL-102 (Shin-EtsuChemical Co., Ltd.) having a carbon content of 80 wt % was deposited toa thickness of 200 nm and a silicon-containing spin-on hard maskSHB-A940 having a silicon content of 43 wt % was deposited thereon to athickness of 35 nm. On this substrate for trilayer process, each of theresist compositions in Table 1 was spin coated, then baked on a hotplate at 100° C. for 60 seconds to form a resist film of 80 nm thick.

Using an ArF excimer laser immersion lithography scanner NSR-S610C(Nikon Corp., NA 1.30, σ 0.98/0.78, 35° cross-pole illumination,azimuthally polarized illumination), the resist film was exposed througha 6% halftone phase shift mask bearing a pattern having a line of 60 nmand a pitch of 200 nm (on-wafer size). The resist film was baked (PEB)at the temperature shown in Table 1 for 60 seconds and immediatelydeveloped in n-butyl acetate for 30 seconds, yielding a negative trenchpattern having a space of 60 nm and a pitch of 200 nm.

In another run, the same procedure as above was followed until theexposure and PEB steps. The resist film was stored in a FOUP at 23° C.for 24 hours before it was developed in n-butyl acetate for 30 seconds,yielding a negative trench pattern at a pitch of 200 nm.

Trench pattern size was measured under a scanning electron microscope(SEM) CG-4000 (Hitachi High-Technologies Corp.). The difference betweenthe size of the trench pattern printed by the continuous procedure fromcoating to development and the size of the trench pattern printedthrough 24-hour storage (or delay) after PEB is reported as PPD size.

The results are shown in Table 1.

TABLE 1 Acid Water-repellent Organic PEB PPD Polymer generator Quencherpolymer solvent temp. Sensitivity size (pbw) (pbw) (pbw) (pbw) (pbw) (°C.) (mJ/cm²) (nm) Example 1-1 Polymer 1 PAG1 Quencher 1 Water-repellentPGMEA(2,200) 95 39 0.1 (100) (8.0) (2.50) polymer 1 GBL(300) (4.0) 1-2Polymer 1 PAG1 Quencher 2 Water-repellent PGMEA(2,200) 95 42 0 (100)(8.0) (2.50) polymer 1 GBL(300) (4.0) 1-3 Polymer 1 PAG1 Quencher 3Water-repellent PGMEA(2,200) 95 38 0.1 (100) (8.0) (2.50) polymer 1GBL(300) (4.0) 1-4 Polymer 1 PAG1 Quencher 4 Water-repellentPGMEA(2,200) 95 36 0 (100) (8.0) (2.20) polymer 1 GBL(300) (4.0) 1-5Polymer 1 PAG1 Quencher 5 Water-repellent PGMEA(2,200) 95 37 0.1 (100)(8.0) (2.10) polymer 1 GBL(300) (4.0) 1-6 Polymer 1 PAG1 Quencher 6Water-repellent PGMEA(2,200) 95 38 0.2 (100) (8.0) (2.50) polymer 1GBL(300) (4.0) 1-7 Polymer 1 PAG1 Quencher 7 Water-repellentPGMEA(2,200) 95 41 0.1 (100) (8.0) (2.50) polymer 1 GBL(300) (4.0) 1-8Polymer 1 PAG1 Quencher 8 Water-repellent PGMEA(2,200) 95 39 0 (100)(8.0) (3.10) polymer 1 GBL(300) (4.0) 1-9 Polymer 1 PAG1 Quencher 9Water-repellent PGMEA(2,200) 95 40 0 (100) (8.0) (3.50) polymer 1GBL(300) (4.0) 1-10 Polymer 3 PAG1 Quencher 10 Water-repellentPGMEA(2,200) 95 41 0 (100) (8.0) (2.90) polymer 1 GBL(300) (4.0) 1-11Polymer 2 — Quencher 10 Water-repellent PGMEA(2,200) 100 44 0 (100)(2.50) polymer 1 GBL(300) (4.0) 1-12 Polymer 2 — Quencher 11Water-repellent PGMEA(2,200) 100 44 0 (100) (2.10) polymer 1 GBL(300)(4.0) 1-13 Polymer 2 — Quencher 12 Water-repellent PGMEA(2,200) 100 46 0(100) (2.10) polymer 1 GBL(300) (4.0) 1-14 Polymer 2 — Quencher 13Water-repellent PGMEA(2,200) 100 48 0 (100) (2.10) polymer 1 GBL(300)(4.0) Comparative 1-1 Polymer 1 PAG1 Comparative Water-repellentPGMEA(2,200) 95 55 1.3 Example (100) (8.0) Quencher 1 polymer 1 GBL(300)(3.13) (4.0) 1-2 Polymer 1 PAG1 Comparative Water-repellent PGMEA(2,200)95 56 1.5 (100) (8.0) Quencher 2 polymer 1 GBL(300) (3.13) (4.0) 1-3Polymer 1 PAG1 Comparative Water-repellent PGMEA(2,200) 95 45 0.8 (100)(8.0) Quencher 3 polymer 1 GBL(300) (4.50) (4.0) 1-4 Polymer 1 PAG1Comparative Water-repellent PGMEA(2,200) 95 44 0.6 (100) (8.0) Quencher4 polymer 1 GBL(300) (4.50) (4.0) 1-5 Polymer 1 PAG1 ComparativeWater-repellent PGMEA(2,200) 95 55 0.5 (100) (8.0) Quencher 5 polymer 1GBL(300) (4.50) (4.0)EB Writing Test

Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-5

Each of the resist compositions in Table 2 was spin coated onto asilicon substrate, which had been vapor primed with hexamethyldisilazane(HMDS), and pre-baked on a hot plate at 110° C. for 60 seconds to form aresist film of 80 nm thick. Using a system HL-800D (Hitachi Ltd.) at anaccelerating voltage of 50 kV, the resist film was exposed imagewise toEB in a vacuum chamber. Immediately after the image writing, the resistfilm was baked (PEB) on a hot plate at 90° C. for 60 seconds anddeveloped in a 2.38 wt % TMAH aqueous solution for 30 seconds to form apattern. The resist pattern was evaluated as follows.

In the case of positive resist film, the resolution is a minimum trenchsize at the exposure dose that provides a resolution as designed of a120-nm trench pattern. In the case of negative resist film, theresolution is a minimum isolated line size at the exposure dose thatprovides a resolution as designed of a 120-nm isolated line pattern. Itis noted that Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-3,2-5 are positive resist compositions, and Example 2-5 and ComparativeExample 2-4 are negative resist compositions.

The results are shown in Table 2.

TABLE 2 Acid Organic Polymer generator Base solvent SensitivityResolution LWR (pbw) (pbw) (pbw) (pbw) (μC/cm²) (nm) (nm) Example 2-1Polymer 4 — Quencher 8 PGMEA(400) 32 75 3.0 (100) (1.80) CyH(2,000)PGME(100) 2-2 Polymer 4 — Quencher 9 PGMEA(400) 33 75 3.1 (100) (1.80)CyH(2,000) PGME(100) 2-3 Polymer 4 — Quencher 10 PGMEA(400) 35 75 3.0(100) (1.90) CyH(2,000) PGME(100) 2-4 Polymer 5 PAG2 Quencher 8PGMEA(400) 36 80 3.3 (100) (15.0) (1.80) CyH(1,600) CyP(500) 2-5 Polymer6 PAG3 Quencher 8 PGMEA(2,000) 36 75 3.9 (100) (10.0) (1.80) CyH(500)Comparative 2-1 Polymer 4 — Comparative PGMEA(400) 38 90 4.5 Example(100) Quencher 1 CyH(2,000) (2.50) PGME(100) 2-2 Polymer 4 — ComparativePGMEA(400) 38 90 4.6 (100) Quencher 2 CyH(2,000) (2.50) PGME(100) 2-3Polymer 4 — Comparative PGMEA(400) 38 90 4.2 (100) Quencher 3 CyH(2,000)(2.50) PGME(100) 2-4 Polymer 6 PAG1 Comparative PGMEA(2,000) 38 85 5.2(100) (10.0) Quencher 3 CyH(500) (2.50) 2-5 Polymer 4 — ComparativePGMEA(400) 44 90 4.3 (100) Quencher 5 CyH(2,000) (2.50) PGME(100)

It is demonstrated in Tables 1 and 2 that resist compositions comprisinga phosphazene salt compound offer dimensional stability on PPD and asatisfactory resolution and LWR.

Japanese Patent Application Nos. 2015-256346 and 2016-135025 areincorporated herein by reference.

Although some preferred embodiments have been described, manymodifications and variations may be made thereto in light of the aboveteachings. It is therefore to be understood that the invention may bepracticed otherwise than as specifically described without departingfrom the scope of the appended claims.

The invention claimed is:
 1. A resist composition comprising a basepolymer and a phosphazene salt compound having the formula (A):

wherein R¹ to R⁷ are each independently hydrogen, or a C₁-C₂₄ straight,branched or cyclic alkyl group, C₂-C₂₄ straight, branched or cyclicalkenyl group, C₂-C₂₄ straight, branched or cyclic alkynyl group, orC₆-C₂₀ aryl group, which may contain an ester, ether, sulfide,sulfoxide, carbonate, carbamate, sulfone, halogen, amino, amide,hydroxy, thiol or nitro moiety, a pair of R¹ and R², R² and R³, R³ andR⁴, R⁴ and R⁵, R⁵ and R⁶, or R⁶ and R⁷ may bond together to form a ring,or a pair of R² and R³, R⁴ and R⁵, or R⁶ and R⁷, taken together, mayform a double bond or a group having the formula (A)-1, R¹ may be agroup having the formula (A)-2,

wherein R⁸ to R¹⁷ are each independently hydrogen, or a C₁-C₂₄ straight,branched or cyclic alkyl group, C₂-C₂₄ straight, branched or cyclicalkenyl group, C₂-C₂₄ straight, branched or cyclic alkynyl group, orC₆-C₂₀ aryl group, a pair of R⁸ and R⁹, R⁹ and R¹⁰, R¹⁰ and R¹¹, R¹¹ andR¹², R¹² and R¹³, R¹⁴ and R¹⁵, or R¹⁶ and R¹⁷ may bond together to forma ring, or a pair of R⁸ and R⁹, R¹⁰ and R¹¹, or R¹² and R¹³, takentogether, may form a double bond or a group having the formula (A)-1, A⁻is an anion selected from the group consisting of hydroxide, chloride,bromide, iodide, nitrate, nitrite, chlorate, chlorite, perchlorate,hydrogencarbonate, dihydrogenphosphate, hydrogensulfate, thiocyanate,hydrogenoxalate, cyanide, iodate ions, and anions of the formulae (M-1)and (M-2):

wherein R¹⁸ is hydrogen, or a C₁-C₃₀ straight, branched or cyclic alkylgroup, C₂-C₃₀ straight, branched or cyclic alkenyl group, C₂-C₃₀straight, branched or cyclic alkynyl group, C₆-C₂₀ aryl group, C₇-C₂₀aralkyl group, or C₃-C₂₀ aromatic or aliphatic heterocycle-containinggroup, which may contain an ester, ether, sulfide, sulfoxide, carbonate,carbamate, sulfone, halogen, amino, amide, hydroxy, thiol or nitromoiety, with the proviso that R¹⁸ does not contain a group of theformula (A)-3:

wherein Ar is a C₆-C₁₆ aromatic group, R²¹ and R²² are eachindependently hydrogen, hydroxy, alkoxy, C₁-C₆ straight, branched orcyclic alkyl group, or C₆-C₁₀ aryl group, R¹⁹ is fluorine, or a C₁-C₁₀straight, branched or cyclic fluoroalkyl group or fluorophenyl group,which may contain a hydroxy, ether, ester or alkoxy moiety, R²⁰ ishydrogen, or a C₁-C₁₀ straight, branched or cyclic alkyl group, C₂-C₁₀straight, branched or cyclic alkenyl group, C₂-C₁₀ straight or branchedalkynyl group, or C₆-C₁₀ aryl group, which may contain a hydroxy, ether,ester or alkoxy moiety, wherein the carboxylate anion having formula(M-1) is selected from the group consisting of the following formulae:


2. The resist composition of claim 1, further comprising an acidgenerator capable of generating sulfonic acid, sulfonimide orsulfonmethide.
 3. The resist composition of claim 1, further comprisingan organic solvent.
 4. The resist composition of claim 1 wherein thebase polymer comprises recurring units having the formula (a1) orrecurring units having the formula (a2):

wherein R³¹ and R³³ are each independently hydrogen or methyl, R³² andR³⁴ are each independently an acid labile group, X is a single bond,ester group, phenylene group, naphthylene group or a C₁-C₁₂ linkinggroup containing lactone ring, and Y is a single bond or ester group. 5.The resist composition of claim 4, further comprising a dissolutioninhibitor.
 6. The resist composition of claim 4 which is a chemicallyamplified positive resist composition.
 7. The resist composition ofclaim 1 wherein the base polymer is free of an acid labile group.
 8. Theresist composition of claim 7, further comprising a crosslinker.
 9. Theresist composition of claim 7 which is a chemically amplified negativeresist composition.
 10. The resist composition of claim 1 wherein thebase polymer comprises recurring units of at least one type selectedfrom the formulae (f1) to (f3):

wherein R⁵¹, R⁵⁵ and R⁵⁹ each are hydrogen or methyl, R⁵² is a singlebond, phenylene, —O—R⁶³—, or —C(═O)—Y¹—R⁶³—, Y¹ is —O— or —NH—, R⁶³ is aC₁-C₆ straight, branched or cyclic alkylene or alkenylene group whichmay contain a carbonyl, ester, ether or hydroxyl moiety, or phenylenegroup, R⁵³, R⁵⁴, R⁵⁶, R⁵⁷, R⁵⁸, R⁶⁰, R⁶¹, and R⁶² are each independentlya C₁-C₁₂ straight, branched or cyclic alkyl group which may contain acarbonyl, ester or ether moiety, or a C₆-C₁₂ aryl group, C₇-C₂₀ aralkylgroup or mercaptophenyl group, A¹ is a single bond, -A⁰-C(═O)—O—, -A⁰-O—or -A⁰-O—C(═O)—, A⁰ is a C₁-C₁₂ straight, branched or cyclic alkylenegroup which may contain a carbonyl, ester or ether moiety, A² ishydrogen or trifluoromethyl, Z¹ is a single bond, methylene, ethylene,phenylene, fluorinated phenylene, —O—R⁶⁴—, or —C(═O)—Z²—R⁶⁴—, Z² is —O—or —NH—, R⁶⁴ is a C₁-C₆ straight, branched or cyclic alkylene oralkenylene group which may contain a carbonyl, ester, ether or hydroxylmoiety, or phenylene, fluorinated phenylene ortrifluoromethyl-substituted phenylene group, M⁻ is a non-nucleophiliccounter ion, and f1, f2 and f3 are numbers in the range: 0≤f1≤0.5,0≤f2≤0.5, 0≤f3≤0.5, and 0<f1+f2+f3≤0.5.
 11. The resist composition ofclaim 1, further comprising a surfactant.
 12. A process for forming apattern comprising the steps of applying the resist composition of claim1 onto a substrate, baking to form a resist film, exposing the resistfilm to high-energy radiation, and developing the exposed film in adeveloper.
 13. The process of claim 12 wherein the high-energy radiationis ArF excimer laser radiation of wavelength 193 nm or KrF excimer laserradiation of wavelength 248 nm.
 14. The process of claim 12 wherein thehigh-energy radiation is electron beam or extreme ultraviolet radiationof wavelength 3 to 15 nm.
 15. A resist composition comprising a basepolymer and a phosphazene salt compound having the formula (A):

wherein R¹ to R⁷ are each independently hydrogen, or a C₁-C₂₄ straight,branched or cyclic alkyl group, C₂-C₂₄ straight, branched or cyclicalkenyl group, C₂-C₂₄ straight, branched or cyclic alkynyl group, orC₆-C₂₀ aryl group, which may contain an ester, ether, sulfide,sulfoxide, carbonate, carbamate, sulfone, halogen, amino, amide,hydroxy, thiol or nitro moiety, a pair of R¹ and R², R² and R³, R³ andR⁴, R⁴ and R⁵, R⁵ and R⁶, or R⁶ and R⁷ may bond together to form a ring,or a pair of R² and R³, R⁴ and R⁵, or R⁶ and R⁷, taken together, mayform a double bond or a group having the formula (A)-1, R¹ may be agroup having the formula (A)-2,

wherein R⁸ to R¹⁷ are each independently hydrogen, or a C₁-C₂₄ straight,branched or cyclic alkyl group, C₂-C₂₄ straight, branched or cyclicalkenyl group, C₂-C₂₄ straight, branched or cyclic alkynyl group, orC₆-C₂₀ aryl group, a pair of R⁸ and R⁹, R⁹ and R¹⁰, R¹⁰ and R¹¹, R¹¹ andR¹², R¹² and R¹³, R¹⁴ and R¹⁵, or R¹⁶ and R¹⁷ may bond together to forma ring, or a pair of R⁸ and R⁹, R¹⁰ and R¹¹, or R¹² and R¹³, takentogether, may form a double bond or a group having the formula (A)-1, A⁻is an anion selected from the group consisting of hydroxide, chloride,bromide, iodide, nitrate, nitrite, chlorate, chlorite, perchlorate,hydrogencarbonate, dihydrogenphosphate, hydrogensulfate, thiocyanate,hydrogenoxalate, cyanide, iodate ions, and anions of the formulae (M-1)and (M-2):

wherein R¹⁸ is hydrogen, or a C₁-C₃₀ straight, branched or cyclic alkylgroup, C₂-C₃₀ straight, branched or cyclic alkenyl group, C₂-C₃₀straight, branched or cyclic alkynyl group, C₆-C₂₀ aryl group, or C₇-C₂₀aralkyl group, which may contain an ester, ether, sulfide, sulfoxide,carbonate, carbamate, sulfone, halogen, amino, amide, hydroxy, thiol ornitro moiety, with the proviso that R¹⁸ does not contain a group of theformula (A)-3:

wherein Ar is a C₆-C₁₆ aromatic group, R²¹ and R²² are eachindependently hydrogen, hydroxy, alkoxy, C₁-C₆ straight, branched orcyclic alkyl group, or C₆-C₁₀ aryl group, R¹⁹ is fluorine, or a C₁-C₁₀straight, branched or cyclic fluoroalkyl group or fluorophenyl group,which may contain a hydroxy, ether, ester or alkoxy moiety, R²⁰ ishydrogen, or a C₁-C₁₀ straight, branched or cyclic alkyl group, C₂-C₁₀straight, branched or cyclic alkenyl group, C₂-C₁₀ straight or branchedalkynyl group, or C₆-C₁₀ aryl group, which may contain a hydroxy, ether,ester or alkoxy moiety.
 16. The resist composition of claim 15 whereinthe base polymer comprises recurring units having the formula (a1) orrecurring units having the formula (a2):

wherein R³¹ and R³³ are each independently hydrogen or methyl, R³² andR³⁴ are each independently an acid labile group, X is a single bond,ester group, phenylene group, naphthylene group or a C₁-C₁₂ linkinggroup containing lactone ring, and Y is a single bond or ester group.17. The resist composition of claim 16 which is a chemically amplifiedpositive resist composition.
 18. The resist composition of claim 15wherein the base polymer is free of an acid labile group.
 19. The resistcomposition of claim 18 which is a chemically amplified negative resistcomposition.
 20. A process for forming a pattern comprising the steps ofapplying the resist composition of claim 15 onto a substrate, baking toform a resist film, exposing the resist film to high-energy radiation,and developing the exposed film in a developer.